Dr.

Subhabrata Banerjee
Associate Professor
Department of Chemistry
Ramakrishna Mission V. C. College, Rahara
 SYLLABUS
Semester – II / MCP - 06

Dr. S. Banerjee, RKMVCC, Rahara

Unit-2.Spectroscopy : 18M: (16-20L)
Underlining Principles: Electromagnetic radiation and its interaction with
matter- absorption, emission, transmission, reflection , refraction, dispersion,
polarization and scattering. Uncertainty relation, natural line width and
natural line broadening; results of time dependent perturbation theory-
transition probability, transition moment, selection rules, intensity of spectral
lines; Born-Oppenheimer approximation: rotational, vibrational and electronic
energy levels.
Infrared spectroscopy: Review of linear harmonic oscillator, vibrational
energies of diatomic molecules, zero point energy, force constant and bond
strengths; anharmonicity. Mores potential energy diagram, vibration-rotation
spectroscopy, P,Q,R branches. Breakdown of Born-Oppenheimer
approximation, vibration of polyatomic molecules. Selection rules, normal
modes of vibration, group frequencies, overtones, hot bands, factor affecting
the band positions and intensities, far IR region, metal-ligand vibrations.
normal coordinate analysis.

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 SYLLABUS

Semester – II / MCP - 06

Dr. S. Banerjee, RKMVCC, Rahara

Unit-2.Spectroscopy : 18M: (16-20L)
Raman spectroscopy: Classical and quantum theories of Raman effect. Pure
rotational, vibrational and vibrational-rotational Raman spectra, selection
rules, mutual exclusion principle.
Molecular Spectroscopy: Energy levels of molecular orbitals, vibronic
transitions,vibrational progressions and geometry of excited states, Frank-
Condon principle, electronic spectra of polyatomic molecules. Emission
Spectra: radiative and non radiative decay, internal conversion, spectra of
transition metal complexes , charge transfer spectra.
Microwave Spectroscopy: Classification of molecules, rigid rotor model,
effect of isotopic substitution on transition frequencies, intensities, non-
rigid rotor. Applications

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 Spectroscopy is the branch of science which deals with the
interaction of electromagnetic radiation with atoms and
molecules. The interaction of electromagnetic radiation with
molecules is known as Molecular Spectroscopy.

Dr. S. Banerjee, RKMVCC, Rahara

A molecule moving in space can possess different forms of
energy

Translational energy, Etrans

Rotational energy, Erot
Vibrational energy, Evib
Electronic energy, Eelec

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 Molecular Spectroscopy
E2

Dr. S. Banerjee, RKMVCC, Rahara

or
E = E2 – E1 = h

E1
Depending on the region of electromagnetic radiation to
which  belongs, the spectroscopy is named after that.
Molecular spectroscopy is much more complicated than Atomic Spectroscopy

Total energy of the molecule, E = Etrans + Erot + Evib + Eelec

(BORN – OPPENHEIMER approximation)

Generally, Etrans << Erot << Evib << Eelec

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 Molecular Spectroscopy

Dr. S. Banerjee, RKMVCC, Rahara 6

 Pure Microwave Spectroscopy
Or, Pure Rotational Spectroscopy

Let us consider a molecule which is undergoing only

Dr. S. Banerjee, RKMVCC, Rahara

rotational motion (and nothing else) !!

Think of any imaginary axis passing through the body, about which
the body can rotate. This axis is termed as rotational axis

It is convenient to consider
a set of three mutually
perpendicular axes, each
passing through the center
of gravity of the body.
They are called the
principal axes of
rotation.

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 Pure Rotational Spectroscopy

1 2
Classical expression of rotational energy for a rotating body = I
2

Dr. S. Banerjee, RKMVCC, Rahara

I = moment of inertia
 is the angular velocity in radian per second

I is defined as the mass of each atom multiplied by the square of its

distance from the rotational axis

I =  mi ri
2

ri is the perpendicular distance of the atom i from the axis of rotation

Conventionally, Ic  IB  IA

Dr. S. Banerjee, RKMVCC, Rahara 8

 Pure Rotational Spectroscopy

Molecules may be classified into groups according to the

relative values of their three principal moments of inertia

Dr. S. Banerjee, RKMVCC, Rahara

1. Linear molecules
IC

C
IA = 0

IB

Evidently, IA = 0. Also, IB = IC

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 Pure Rotational Spectroscopy

2. Symmetric top
IB = IC  IA and IA  0

IB = IC > IA IC > IB = IA
prolate symmetric top Oblate symmetric top

A symmetric rotor must have either a Cn axis with n > 2 or an S4 axis

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Pure Rotational Spectroscopy

3. Spherical top

IA = IB = IC

Dr. S. Banerjee, RKMVCC, Rahara

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 Pure Rotational Spectroscopy

4. Asymmetric top

IA  IB  IC

Dr. S. Banerjee, RKMVCC, Rahara

Examples are H2O, CH3OH, HCHO, etc

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 PURE ROTATIONAL SPECTRA OF DIATOMIC RIGID ROTOR

Here, IA = 0. Also, IB = IC

We need to calculate ONE moment of inertia about

Dr. S. Banerjee, RKMVCC, Rahara

any one of the end – over – end axis

How to calculate moment of inertia for a diatomic molecule ?

C
m1 m2
r2
r1
r0

r0 = r1 + r2
I = m1 r1 + m2 r2
2 2

m1 r1 = m2 r2
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 PURE ROTATIONAL SPECTRA OF DIATOMIC RIGID ROTOR

I = m1 r1 + m2 r2
2 2

Or, I = (m1 r1 )r1 + (m2 r2 )r2

Dr. S. Banerjee, RKMVCC, Rahara

Or, I = (m2 r2 )r1 + (m1 r1 )r2 m1 r1 = m2 r2
Or, I = r1 r2 (m1 + m2 )

m1 r1 = m2 r2
2
m1 m2 r0
Or, I = (m1 + m2 )
(m1 + m2 ) 2
m1 r1 = m2 (r0 − r1 ) r0 = r1 + r2
Or,
m1m2 m2 r0
I= r0 =  .r0 r1 =
2 2
Or, Or,
(m1 + m2 ) m1 + m2
Similarly,
m1 r0
r2 =
m1 + m2

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PURE ROTATIONAL SPECTRA OF DIATOMIC RIGID ROTOR

m1m2
I= r0 =  .r0
2 2

(m1 + m2 )

Dr. S. Banerjee, RKMVCC, Rahara

m1 m2 1 1 1
where,  = Or, = +
(m1 + m2 )  m1 m2

Suppose the atomic weights of the two constituent atoms

are M1 and M2

M1 M2
So, m1 = and, m2 =
NA NA
M1 M 2
m1 m2 NA NA M 1M 2 1
= = Or, =
(m1 + m2 ) M 1 + M 2 M1 + M 2 N A
NA NA

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Dr. S. Banerjee, RKMVCC, Rahara
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